Catalytic system for the addition of bisulfites to olefins



United States Patent Ofilice 3,275,681 Patented Sept. 27, 1966 3,275,681 CATALYTIC SYSTEM FOR THE ADDITION OF BISULFITES TO OLEFINS William S. Emerson, Lexington, Richard N. Macnalr, Cambridge, and Chi-Hua Wang, Lexington, Mass., assignors to Arthur D. Little, Inc., Cambridge, Mass., a corporation of Massachusetts No Drawing. Filed May 20, 1963, Ser. No. 281,797 2 Claims. (Cl. 260-513) This invention relates to a new and improved catalytic system for the promotion of reactions between bisulfite ion and an olefin to form alkylsulfonic acids and their salts.

The reaction is known, but none of the synthesis routes to the product, particularly to long straight chain aliphatic sulfonic acids or to alkylsulfonic acids in general have been adaptable to commercial production.

One prior art method of adding bisulfite to l-olefins of the structure RCH=CH dis-closes carrying out the reaction in any oxygen atmosphere of pressures ranging between 15 and 40 pounds p.s.i.g. to obtain yields from 15% to 90%. Another prior art method carries out the reaction between ammonium bisulfite and an excess of olefin in the presence of sodium nitrite and sodium nitrate to obtain yields of about 20% of theoretical. Finally, U.S.P. 2,398,426 discloses a similar addition reaction of ammonium bisulfite to olefins under elevated pressures and temperatures, e.g., 400 atmospheres and 120 C. using 2,2-bis(t-butylperoxide)butane as a catalyst. Yields by this process were stated to be as high as 96%.

None of these prior art method-s has been satisfactory as a commercial synthesis route for one or more reasons. The need for high. pressures and temperatures in some of these syntheses requires large capital outlay for equipment; while the use of a pressurized gaseous reaction atmosphere requires special equipment and raise problems in the manufacture of a material which is by nature a detergent and which is therefore subject to foaming in the presence of gas capable of extending it. Finally, many of the prior art processes have not been able to achieve yields which make them attractive to commercialization.

Compounds of the general formula RCH CH SO H and their salts are known to be effective detergents, textile softening agents, emulsifying agents, and the like. However, it is in the detergent field that they offer the most interesting possibility since they are stable under all pHs and particularly stable toward acidic conditions due to the fact that the sulfur atom is attached directly to the carbon chain. Even more important, however, is the fact that the presence of the long straight aliphatic chain makes these materials biodegradable. This latter characteristic is of particular importance in view of the fact that it has now become a worldwide problem to develop detergents which can be removed from sewage. At the present time, sulfonates which are not biodegradableat least no biological bodies are known at present which are capable of degrading these detergents to remove them in subsequent water repurification processes.

The method of this invention may be briefly described as adding the bisulfite ion to olefinic compounds at room temperature in the presence of a catalyst which may be defined as comprising a peroxide and an organometal salt, the metal of which is capable of undergoing a change in valence state by single electron transfer process.

many of the detergents used are aromatic The invention, accordingly, comprises the several steps and the relation of one or more of such steps with respect to each of the others thereof, which will be exemplified in the method hereinafter disclosed, and the scope of the invention will be indicated in the claims.

It is a primary object of this invention to provide a new and improved catalytic system for the promotion of the reaction between a bisulfite ion and an olefin. It is another object of this invention to provide an improved catalytic system of the character described which is capable of catalyzing the reaction at room temperatures and ambient pressures. It is yet another object to provide such a catalytic system which is capable of effecting the reaction indicated in a continuous process to obtain an overall good yield. It is yet another object to provide such a catalytic ssytem which permits the reaction to be carried out without any attendant complications, and in standard equipment which does not require the outlay of large amounts of capital or the design of special apparatus.

It is another primary object of this invention to make available on -a commercial scale alkylsulfonic acids and their salts which are particularly well suited as detergents, the detergents being biodegradable. Other objects of the invention will in part be obvious and will in part be apparent hereinafter.

The addition of bisulfite to olefins through free radical exchange has been well established to involve the following chain process (J. Org. Chem. 3 (1938)):

By the method of this invention the process is catalyzed by a redox system which can be expressed generally as M+++ROOR- M+++-|-OR+-OR Where M is a metal and R is below.

The reaction is carried out in a liquid medium and at temperatures which may range from as low as -10 C. to room temperature or above. It is, moreover, adaptable to a continuous process operation in which the product is removed as formed and the unreacted components returned for further reaction in the presence of fresh catalyst. Thus, yields over a period of time may be kept high without resorting to undersirable reaction condi-tions such as extremely high temperatures and pressures or the use of a gas which would cause the product to foam.

The olefin component to which the bisulfite is added may be generally defined as one having the formula H H Elke-R the one restriction on R being that it does not result in an olefinic compound which is conjugated with a heterounsaturated group such as C=O, cyano and the like. Thus, R may be hydrogen, alkyl, substituted alkyl, or part of an unconjugated cyclic grouping. The substituent on the alkyls may be halogens, aryl groups, and the like. Where R is alkyl the carbon chain may be any length required to give the final alkylsulfonic acid or salt the properties desired of it. Thus, propene, butene, isoprene, octene, dodecene, as well as the alkyl groups formed of very long carbon chains are all suitable since steric hindrance is not a problem, and the reactive site is not influenced by the length of the R chain. i-phenyl-l-butene may be cited as an example of an aryl-substituted alkyl olefin and cyclohexene as an example where the C=C grouping is part of a cyclic structure.

a suitable group defined The source of the bisulfite ion should be the salt of a strong base since at ambient conditions the use of a salt of a weak base would lead to an undesirable amount of hydrolysis. The alkali met-a1 bisulfites are the most suit The use of peroxide and organometallic salt concentra tions much below 0.2 mol percent of the olefin result in low yields, probably because of the difficulties inherent in thoroughly and uniformly mixing such small quanable, with sodium bisulfite being generally preferred. 5 tities throughout the liquid reaction medium.

The liquid medium in which the reatcion is carried out Although there is nothing critical in the manner in and which contains the catalytic system is a mixture of which the reactants and catalytic system are mixed, the water and a water-miscible organic liquid which is a solbisulfite is preferably dissolved in water, the olefin in vent for the olefin. The inorganic bisulfites are soluble the organic solvent, and the peroxide and organometallic in the water portion and the olefins in the organic solvent salt making up the catalytic system in the organic .phase. which means that at the beginning of the reaction there The two phases are then mixed thoroughly and stirred for is actually a two-phase system. The ratio of water to that period of time required to give the yield desired. In organic solvent is not critical so long as there is sufficient a batch process this may be a day or two, while in a conquantities of both liquids to dissolve the bisulfite and Oletinuous process the mixing and continual addition of fresh fin reactants. catalyst and withdrawal of product can be carried out.

The water-miscible organic solvents include, but are The product formed by the reaction is, of course, a not limited to, the lower aliphatic alcohols (methyl, ethyl, sal the cation of which is the cation of the inorganic n-propyl and isopropyl) tetrahydrofuran, dimethyltor bisulfite reactant. This salt is normally soluble in water, amide and the like. and must therefore be isolated. This may be done by In the catalytic system the peroxide, represented by the removing the liquid reaction medium by well-known general f l R'Q OR" i a id which i h techniques such as distillation at reduced pressures, or ble in the oil phase of the reaction medium. R and R" by spray drying. The salt may be precipitated as an may be hydrogen, racy], alkyl, .aryl-alkyl or aroyl, Both insoluble salt such as the lead salt by adding lead acetate R and R" may not, ho ever, be h d th 1i i t to the solution for example. The 'free alkylsulfonic acids ing hydrogen peroxide. Acetyl peroxide i a example may be isolated but they are extremely hygroscopic. This of a suitable peroxide in which R and R" are acyl; tery he done y acidifying the liquid reaction medium, tiary butyl hydroperoxide of a peroxide where R is alkyl concentrating i under reduced Pressure and extracting and R" hydrogen; cumene hydroperoxide Where R is an the aikyisnifenie acids with P PY aieehol- 1 1k 1 d R" i h d d b l id The process of this invention may be further described wh R d R" are b th l, S i bl b i d with reference to the following examples which are peroxides may also be usedfor example, p,p'chlorobenmeant to he illustrative and not limitingzoyl peroxide is typical of a substituted diaroyl peroxide. A number of olefins were caused to react h inor- The organometal portion of the catalytic system may genie bisulfites Sing Various catalytic y The be defined as a metal organic in which the metal is one Specific date on these are tabulated heiow- In carrying which is capable f undergoing a change i valehce State 3 out these reactions the bisulfite and olefin were stirred into by a single electron transfer process. This catalyst coma water/methanol iiqnid reaction medium which was a ponent should be solubl i th o i phase f h mixture of 30 ml. Water and 300ml. methanol and which reaction medium. Among the metals which meet this Contained the Peroxide organometaiiie Salt the requirement are the transition metals including iron, mancatalyst y The IIliXtnfe s Stirred at r m t mganese, titanium, vanadium, cobalt, nickel and the like. 40 Peratnre for n Period of from One to Sevehai y The Among the organometal salts which have been found to Solvent was then removed at reduced Pressure 30 be particularly useful in the catalytic system of this in to leave the Sodium Salt which was an y Solid vention may be listed ferrocene (dicyclopentadienyl iron) residne- Quantitative isolation was eaIfied Out a P cobaltocene (dicyclopentadienyl cobalt), the metal naphtion of each Product by acidifying the water Solution of thenates, and the B-diketone chelates of the transition the Sodium 'aikyisnifenate and precipitating the Snifonie metals. The manganese, vanadium, cobalt, and iron salts acid s its e Salt by the addition of lead acetate- Catalytic System Example Olefin B isulfite Yield, N0 percent Peroxide Organometallie Compound assign the; sari as -Phss a l-octene (0.2) Sodium (.29) do Dicyclopentadienyl iron (0.05) 25 l-hexadecene (0.1) Sodium (0.14) .do Mn salt of acetyl acetonate (0.04) l7 l-dodecene (0.2) Ammonium (0.24)- Cumene hydroperoxide (0.04) Dlcyclopentadienyl iron (0.05) Trace l-octene (0.2) Sodium (0.29). do Ammonium (.2l) Cumene hydroperoxide (0.24) Ferrous sulfate (0.10) 0 1 Numbers in are mols of reactant or catalyst.

of acetyl acetonate are examples of the last-named type It will be seen from the examples which are tabulated of organometal compounds. above that the method of adding a bisulfite ion to olefins In carrying out the reaction between the inorganic bi- 6r is applicable to those olefins wherein the R of the olefinic sulfite and olefin the reactants may be employed in the structure represented y stoichiometric ratio of one mole of bisulfite to one mole H H of olefin. An excess of either reactant is not detrimental, but it is preferable to use an excess of the inorganic bib 1k f sulfite if stoichiometric quantities are not used. 7 may 6 a Y1 O varying length or the C=C grouping The amount of the components making up the catalytic system may be conveniently expressed as mol percent of the olefin reactant. Peroxide and organometallic salt concentrations above about 0.25 mol percent of the olefin do not enhance therate of reactions or percent yield. 7

may be present in a cyclic unconjugated structure such as in cyclohexene. These data also illustrate the use of various peroxides and metalorgano compounds which meet the requirements stated above.

Examples 6 and 7 are controls, 6 showing that no reaction takes place between an olefin and a bisulfite in the absence of a catalytic system and 7 illustrates the ineffectiveness of the catalytic system when the metal ion is present as a water-soluble inorganic salt.

Finally, Example 4 illustrates the fact that when the alkyl portion of the olefin is extremely long (in this case a carbon chain of 16 carbon atoms) the yields are not as high as in the case of octene for example. This is apparently due to the fact that the olefins having the longer canbon chains are less soluble in the water-miscible organic liquid and hence a smaller amount of the olefin is available for reaction. These smaller yields may be overcome at least to some extent by suitable choice of solvent, and the use of more dilute solutions.

It will be seen from the above description of the method of this invention and from the examples that there is provided a novel catalytic system which permits the addition of bisulfite ions to olefins at room temperatures. Since the reaction does not require elevated temperatures or pressures, nor the use of gaseous atmospheres (e.g., oxygen) it is possible to efiiciently and economically form alkylsulfonic acids and their derivatives either by a batch or continuous process.

It will thus be seen that the objects set forth, among those made is apparent from the preceding description are efliciently attained and since certain changes may be made in carrying out the above method without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

We claim:

1. A method of adding the bisulfite ion to an olefin, consisting essentially of the step of reacting an inorganic alkali-metal bisulfite dissolved in an aqueous liquid with an olefin of the formula RCH=CH wherein R is alkyl, dissolved in a water-miscible organic liquid; said reacting being in the presence of a catalytic system insoluble in Water and soluble in said organic liquid, said catalytic system consisting essentially of an organic peroxide of the formula ROOR", wherein R and R are selected from the group consisting of hydrogen, acyl, alkyl, and aryl-alkyl, and a water-insoluble organometallic compound of a transition metal M which is a fl-diketone chelate of said metal or a dicyclopentadienyl of said metal, whereby said catalytic system gives rise to a reaction generally expressed as 2. A method of reacting an inorganic bisulfite with an olefin thereby to effect the addition of a bisulfite ion to an olefin, consisting essentially of the steps of (a) dissolving an alkali metal bisulfite in Water to form a first phase;

(b) at least partially dissolving an olefin of the formula RCH=CH wherein R is alkyl, in a Water-miscible organic liquid to form a second phase;

(c) mixing at room temperature said first and second phases in the presence of a catalytic system soluble in said second phase and consisting essentially of dibenzoyl peroxide and dicyclopentadienyl iron or a manganese salt of acetyl acetonate; and

(d) isolating the resulting olefinic bisulfite.

References Cited by the Examiner UNITED STATES PATENTS 2,318,036 4/ 1943 Werntz 260*513 FOREIGN PATENTS 1,087,994 3/1955 France.

OTHER REFERENCES Kharasch et al.: J. Org. Chem, vol. 1.5, 1950, pp. 763- 774.

Kharasch et aL: J. Am. Chem. Soc., vol. 81, 1959, pp. 5819-5824.

LORRAINE A. WEINBERGER, Primary Examiner.

LEON ZITVER, B. M. EISEN, M. WEBSTER,

Examiners. 

1. A METHOD OF ADDING THE BISULFITE ION TO AN OLEFIN, CONSISTING ESSENTIALLY OF THE STEP OF REACTING AN INORGANIC ALKALI-METAL BISULFITE DISSOLVED IN AN AQUEOUS LIQUID WITH AN OLEFIN OF THE FORMULA R-CH=CH2, WHEREIN R IS ALKYL, DISSOLVED IN A WATER-MISCIBLE ORGANIC LIQUID; SAID REACTING BEING IN THE PRESENCE OF A CATALYTIC SYSTEM INSOLUBLE IN WATER AND SOLUBLE IN SAID ORGANIC LIQUID, SAID CATALYTIC SYSTEM CONSISTING ESSENTIALLY OF AN ORGANIC PEROXIDE OF THE FORMULA R''O-OR", WHEREIN R'' AND R" ARE SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ACYL, ALKYL, AND ARYL-ALKYL, AND A WATER-INSOLUBLE ORGANOMETALLIC COMPOUND OF A TRANSITION METAL M WHICH IS A B-DIKETONE CHELATE OF SAID METAL OR A DICYCLOPENTADIENYL OF SAID METAL, WHEREBY SAID CATALYTIC SYSTEM GIVES RISE TO A REACTION GENRERALLY EXPRESSED AS 